EP0354843B1 - Process for the preparation of alkyl or alkaline earth ferrates by the solid phase - Google Patents
Process for the preparation of alkyl or alkaline earth ferrates by the solid phase Download PDFInfo
- Publication number
- EP0354843B1 EP0354843B1 EP19890402241 EP89402241A EP0354843B1 EP 0354843 B1 EP0354843 B1 EP 0354843B1 EP 19890402241 EP19890402241 EP 19890402241 EP 89402241 A EP89402241 A EP 89402241A EP 0354843 B1 EP0354843 B1 EP 0354843B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkaline
- process according
- alkali
- mesh size
- granules
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
- C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Definitions
- the invention relates to a process for the preparation of alkali or alkaline earth metal ferrates by reaction of a hypochlorite on an iron compound at most trivalent in the presence of alkali or alkaline earth hydroxides.
- the alkaline and alkaline-earth ferrates, FeO4Na2, FeO4K2, FeO4Ca, FeO4Ba, are powerful oxidants, usable in particular for bleaching textiles, treating waste water, in organic or mineral chemistry processes.
- the object of the invention is a process for the preparation of alkali or alkaline-earth ferrates which eliminates the need to precipitate the ferrate by concentration of the alkali solution, and the losses in yield which the decomposition of ferrate entails during recovery operations.
- the invention provides a process for the preparation of alkali or alkaline earth metal ferrates by reaction of a hypochlorite on an iron compound at most trivalent in the presence of alkali or alkaline earth hydroxides, characterized in that a mixture of an iron (II) or (III) salt and an alkali or alkaline earth metal hypochlorite is made, into a powder passing through a first mesh, a first layer of this powder mixture is formed in a flat receptacle coupled to a mechanical vibration generator, a second layer is formed on this first layer formed of alkali or alkaline earth metal hydroxide granules containing between 10 and 30% by weight of water, the granules being refused in a second mesh clearly larger than the first, the receptacle is subjected to a vibration for 10 to 60 minutes at less than 40 ° C., so that ferrate is formed in contact with the granules, the powdered residues are eliminated p ar sieving to an intermediate mesh
- the ferrate is formed in contact with the hydroxide granules, while the pulverulent phase is eliminated. Furthermore, the ferrate is separated from the hydroxide by dissolving the latter in the organic solvent, under conditions such that the ferrate undergoes practically no decomposition.
- the recovery of the hydroxide from the washing solution is economical with regard to the recovery of hydroxide from an aqueous solution, the latent energy of vaporization of the organic solvents being much lower than that of the water, and so is the latent energy of crystallization of the hydroxide.
- the ground material is spread in a layer, on which 100 parts of commercial potash pellets are dispersed with 15% water; the whole is placed on a vibrator to ensure that the powder / tablet contact is renewed for a period of 10 to 60 minutes, depending on the humidity of the atmosphere. Care is taken that the temperature of the reactive layers does not exceed 40 ° C.
- the reactive mass is sieved with a 1 mm mesh to remove the powder (ferrous sulfate, hypochlorite) which has not reacted. Then the pellets are steamed at a temperature of 105-140 ° C for a period of 8 to 18 hours, at substantially constant weight; in the presence of water, the ferrate is not very stable, and tends to decompose giving hydrated ferric hydroxide. In practice, we will oven at 120 ° C for 12 hours.
- the residual product, purple in color, is stable in a closed enclosure. It can be verified by Mössbauer spectroscopy that the iron is substantially exclusively at the oxidation state VI (singlet of isomeric displacement equal to - 0.88 mm / s relative to metallic iron).
- the ferrate obtained contains salts and hydroxides of potassium and calcium. It can be purified by washing with suitable solvents. In particular dissolved methanol, with potash, potassium and calcium chloride, and potassium carbonate (resulting from air carbonation of caustic potash).
- Tests have made it possible to establish a certain number of practical rules relating to the choice of the iron salt and the operating conditions.
- the start of the reaction required the presence of water but in a limited quantity because the reaction accelerates when the amount of water present increases, and water is formed during the reaction, and by subsequently, water can induce decomposition of the ferrate with the formation of hydroxide.
- the amount of water initially present in the alkali or alkaline earth hydroxide must not be less than 10%, nor more than 30% by weight. It is also necessary to take into account the water of crystallization of the iron salt.
- the iron salt used can be a ferrous salt or a ferric salt.
- ferrous salts are avoided, which are more reducing than ferric salts; by contrast, according to the invention, ferrous salts are preferred, ferric salts in an alkaline medium tending to form ferric hydroxide which catalyzes the decomposition of ferrate, and is difficult to remove.
- the anion is important. Oxidizing anions, such as ferric nitrate, lead to reactions that are difficult to control. Reducing anions, likely to compete with iron in the reaction with hypochlorite, are of course to be avoided. Finally the iron salt must have a significant solubility in bases.
Description
L'invention se rapporte à un procédé de préparation de ferrates de métaux alcalins ou alcalino-terreux par réaction d'un hypochlorite sur un composé de fer au plus trivalent en présence d'hydroxydes alcalins ou alcalino-terreux.The invention relates to a process for the preparation of alkali or alkaline earth metal ferrates by reaction of a hypochlorite on an iron compound at most trivalent in the presence of alkali or alkaline earth hydroxides.
Les ferrates alcalins et alcalino-terreux, FeO₄Na₂, FeO₄K₂, FeO₄Ca, FeO₄Ba, sont des oxydants puissants, utilisables notamment pour le blanchiment de textile, le traitement des eaux usées, dans des processus de chimie organique ou minérale.The alkaline and alkaline-earth ferrates, FeO₄Na₂, FeO₄K₂, FeO₄Ca, FeO₄Ba, are powerful oxidants, usable in particular for bleaching textiles, treating waste water, in organic or mineral chemistry processes.
On a proposé (comme le mentionne JP-A-75926/80) de préparer du ferrate de potassium en attaquant du fer ou de l'oxyde ferrique par un mélange fondu de potasse et nitrate de potassium.It has been proposed (as JP-A-75926/80 mentions) to prepare potassium ferrate by attacking iron or ferric oxide with a molten mixture of potash and potassium nitrate.
On a également proposé (US-A-4 435 256, US-A-4 435 257) de préparer des ferrates, singulièrement du ferrate de sodium, par oxydation électrolytique dans une cellule à membrane, la chambre anodique contenant une solution aqueuse d'hydroxyde de sodium avec un stabilisant du ferrate, et des ions Fe (III), tandis que la chambre cathodique contient une solution aqueuse d'hydroxyde de sodium.It has also been proposed (US-A-4,435,256, US-A-4,435,257) to prepare ferrates, in particular sodium ferrate, by electrolytic oxidation in a membrane cell, the anode chamber containing an aqueous solution of sodium hydroxide with a stabilizer of ferrate, and Fe (III) ions, while the cathode chamber contains an aqueous solution of sodium hydroxide.
On a encore proposé (EP-A-0 082 590) de préparer du ferrate de potassium par réaction, en solution aqueuse à au moins 30 % en poids de potasse très pure, de chlore sur un sel ferrique en présence de silicate de potassium, pour obtenir un précipité d'un mélange de ferrate de potassium, chlorure de potassium et hydroxyde ferrique. Le ferrate est extrait du mélange par dissolution dans une solution de potasse diluée à 5-25 % en poids, après quoi le ferrate est précipité par concentration de la solution de potasse à température comprise entre - 20° et + 20°C.It has also been proposed (EP-A-0 082 590) to prepare potassium ferrate by reaction, in aqueous solution containing at least 30% by weight of very pure potassium hydroxide, of chlorine on a ferric salt in the presence of potassium silicate, to obtain a precipitate of a mixture of potassium ferrate, potassium chloride and ferric hydroxide. The ferrate is extracted from the mixture by dissolving in a potassium solution diluted to 5-25% by weight, after which the ferrate is precipitated by concentration of the potassium solution at a temperature between - 20 ° and + 20 ° C.
Les inconvénients des méthodes précédentes résident dans le fait que les opérations de séparation du ferrate d'avec l'hydroxyde alcalin sont relativement longues, et s'opèrent dans des conditions qui favorisent une décomposition du ferrate, malgré la présence de stabilisants. En outre la concentration des solutions de ferrate dans les alcalis est relativement coûteuse.The disadvantages of the preceding methods reside in the fact that the operations for separating the ferrate from the alkali hydroxide are relatively long, and operate under conditions which favor decomposition of the ferrate, despite the presence of stabilizers. In addition, the concentration of ferrate solutions in alkalis is relatively expensive.
L'invention a pour objectif un procédé de préparation de ferrates alcalins ou alcalino-terreux qui élimine la nécessité de faire précipiter le ferrate par concentration de la solution d'alcali, et les pertes de rendement qu'entraîne la décomposition de ferrate au cours des opérations de récupération.The object of the invention is a process for the preparation of alkali or alkaline-earth ferrates which eliminates the need to precipitate the ferrate by concentration of the alkali solution, and the losses in yield which the decomposition of ferrate entails during recovery operations.
A cet effet, l'invention propose un procédé de préparation de ferrates de métaux alcalins ou alcalino-terreux par réaction d'un hypochlorite sur un composé de fer au plus trivalent en présence d'hydroxydes alcalins ou alcalino-terreux, caractérisé en ce que l'on effectue un mélange d'un sel de fer (II) ou (III) et d'un hypochlorite de métal alcalin ou alcalino-terreux, en poudre passant à une première maille, on forme une première couche de ce mélange en poudre dans un réceptacle plat couplé à un générateur de vibration mécanique, on dépose sur cette première couche une seconde couche formée de granules d'hydroxyde de métal alcalin ou alcalino-terreux contenant entre 10 et 30 % en poids d'eau, les granules étant refusées à une seconde maille nettement plus grande que la première, on soumet le réceptacle à une vibration pendant 10 à 60 minutes à moins de 40°C, en sorte que du ferrate se forme au contact des granules, on élimine les résidus en poudre par tamisage à une maille intermédiaire entre les première et seconde mailles, et on élimine l'excès d'hydroxyde par lavage avec un solvant organique sensiblement anhydre.To this end, the invention provides a process for the preparation of alkali or alkaline earth metal ferrates by reaction of a hypochlorite on an iron compound at most trivalent in the presence of alkali or alkaline earth hydroxides, characterized in that a mixture of an iron (II) or (III) salt and an alkali or alkaline earth metal hypochlorite is made, into a powder passing through a first mesh, a first layer of this powder mixture is formed in a flat receptacle coupled to a mechanical vibration generator, a second layer is formed on this first layer formed of alkali or alkaline earth metal hydroxide granules containing between 10 and 30% by weight of water, the granules being refused in a second mesh clearly larger than the first, the receptacle is subjected to a vibration for 10 to 60 minutes at less than 40 ° C., so that ferrate is formed in contact with the granules, the powdered residues are eliminated p ar sieving to an intermediate mesh between the first and second mesh, and removing excess hydroxide by washing with a substantially anhydrous organic solvent.
Ainsi le ferrate se forme au contact des granules d'hydroxyde, tandis que la phase pulvérulente est éliminée. Par ailleurs, le ferrate est séparé de l'hydroxyde par dissolution de celui-ci dans le solvant organique, dans des conditions telles que le ferrate ne subit pratiquement pas de décomposition.Thus the ferrate is formed in contact with the hydroxide granules, while the pulverulent phase is eliminated. Furthermore, the ferrate is separated from the hydroxide by dissolving the latter in the organic solvent, under conditions such that the ferrate undergoes practically no decomposition.
Accessoirement la récupération de l'hydroxyde à partir de la solution de lavage est économique au regard d'une récupération d'hydroxyde à partir d'une solution aqueuse, l'énergie latente de vaporisation des solvants organiques étant nettement inférieure à celle de l'eau, et il en est de même de l'énergie latente de cristallisation de l'hydroxyde.Incidentally, the recovery of the hydroxide from the washing solution is economical with regard to the recovery of hydroxide from an aqueous solution, the latent energy of vaporization of the organic solvents being much lower than that of the water, and so is the latent energy of crystallization of the hydroxide.
Les caractéristiques secondaires et les avantages de l'invention ressortiront d'ailleurs de la description qui va suivre, illustrée d'exemple.The secondary characteristics and advantages of the invention will become apparent from the description which follows, illustrated by example.
On broie ensemble intimement 100 parties pondérales de sulfate ferreux heptahydraté et 68 parties d'hypochlorite de calcium de qualité commerciale de degré chlorométrique 210, de manière que la masse totale du broyat passe à la maille de 500 µm.100 parts by weight of ferrous sulphate heptahydrate and 68 parts of commercial grade calcium hypochlorite of chlorometric degree 210 are ground together intimately, so that the total mass of the comminuted material becomes 500 µm.
On étale le broyat en couche, sur laquelle on disperse 100 parties de pastilles de potasse commerciale à 15 % d'eau ; le tout est mis sur un vibreur pour assurer que le contact poudre/pastilles se renouvelle pendant une durée de 10 à 60 minutes, selon l'humidité de l'atmosphère. On veille à ce que la température des couches réagissantes ne dépasse pas 40°C.The ground material is spread in a layer, on which 100 parts of commercial potash pellets are dispersed with 15% water; the whole is placed on a vibrator to ensure that the powder / tablet contact is renewed for a period of 10 to 60 minutes, depending on the humidity of the atmosphere. Care is taken that the temperature of the reactive layers does not exceed 40 ° C.
La réaction s'effectue selon la formule suivante :
On notera que, sur les 9 moles d'eau, 7 proviennent du sulfate ferreux, et 2 se forment dans la réduction de l'hypochlorite.Note that, of the 9 moles of water, 7 come from ferrous sulfate, and 2 are formed in the reduction of hypochlorite.
On tamise la masse réactive à la maille de 1 mm pour éliminer la poudre (sulfate ferreux, hypochlorite) qui n'a pas réagi. Puis on étuve les pastilles à une température de 105-140°C pendant une durée de 8 à 18 heures, à poids sensiblement constant ; en présence d'eau, le ferrate est peu stable, et a tendance à se décomposer en donnant de l'hydroxyde ferrique hydraté. Dans la pratique, on étuvera à 120°C pendant 12 heures.The reactive mass is sieved with a 1 mm mesh to remove the powder (ferrous sulfate, hypochlorite) which has not reacted. Then the pellets are steamed at a temperature of 105-140 ° C for a period of 8 to 18 hours, at substantially constant weight; in the presence of water, the ferrate is not very stable, and tends to decompose giving hydrated ferric hydroxide. In practice, we will oven at 120 ° C for 12 hours.
Puis on dissout la potasse en excès par un lavage avec un alcool inférieur, alcool méthylique ou éthylique, avec le moins d'eau possible. L'alcool éthylique est de l'alcool à 96 %.Then the excess potash is dissolved by washing with a lower alcohol, methyl or ethyl alcohol, with as little water as possible. Ethyl alcohol is 96% alcohol.
Le produit résiduel, de couleur pourpre, est stable en enceinte fermée. On peut vérifier par spectroscopie Mössbauer que le fer est sensiblement exclusivement au degré d'oxydation VI (singulet de déplacement isomérique égal à - 0,88 mm/s par rapport au fer métallique).The residual product, purple in color, is stable in a closed enclosure. It can be verified by Mössbauer spectroscopy that the iron is substantially exclusively at the oxidation state VI (singlet of isomeric displacement equal to - 0.88 mm / s relative to metallic iron).
Le ferrate obtenu contient des sels et hydroxydes de potassium et calcium. On peut le purifier par lavage avec des solvants appropriés. Notamment le méthanol dissout, avec la potasse, du chlorure de potassium et de calcium, et du carbonate de potassium (issu de la carbonatation à l'air de la potasse caustique).The ferrate obtained contains salts and hydroxides of potassium and calcium. It can be purified by washing with suitable solvents. In particular dissolved methanol, with potash, potassium and calcium chloride, and potassium carbonate (resulting from air carbonation of caustic potash).
On a vérifié que les hypochlorites de calcium, baryum, sodium et potassium convenaient comme oxydant, et que les hydroxydes de sodium, potassium, calcium et baryum convenaient également, à l'état granulaire, comme base solide réactive. Autrement dit, le choix des métaux alcalins ou alcalino-terreux pour l'oxydant et la base forte est surtout une question d'opportunité, suivant l'utilisation prévue des ferrates et le prix des réactifs.It has been verified that calcium, barium, sodium and potassium hypochlorites are suitable as an oxidant, and that sodium, potassium, calcium and barium hydroxides are also suitable, in granular form, as a reactive solid base. In other words, the choice of alkali or alkaline earth metals for the oxidant and the strong base is above all a question of expediency, depending on the intended use of the ferrates and the price of the reactants.
Des essais ont permis d'établir un certain nombre de règles pratiques relatives au choix du sel de fer et des conditions opératoires.Tests have made it possible to establish a certain number of practical rules relating to the choice of the iron salt and the operating conditions.
Ainsi on a précisé que le démarrage de la réaction exigeait la présence d'eau mais en quantité limitée car la réaction s'accélère lorsque la quantité d'eau présente augmente, et de l'eau se forme au cours de la réaction, et par la suite, l'eau peut induire une décomposition du ferrate avec formation d'hydroxyde. La quantité d'eau présente au départ dans l'hydroxyde alcalin ou alcalino-terreux ne doit pas être inférieure à 10 %, ni supérieure à 30 % en poids. Il y a lieu de prendre en compte également l'eau de cristallisation du sel de fer.Thus it was specified that the start of the reaction required the presence of water but in a limited quantity because the reaction accelerates when the amount of water present increases, and water is formed during the reaction, and by subsequently, water can induce decomposition of the ferrate with the formation of hydroxide. The amount of water initially present in the alkali or alkaline earth hydroxide must not be less than 10%, nor more than 30% by weight. It is also necessary to take into account the water of crystallization of the iron salt.
Le sel de fer utilisé peut être un sel ferreux ou un sel ferrique. Dans la synthèse du ferrate en milieu aqueux on évite les sels ferreux, qui sont plus réducteurs que les sels ferriques ; par contraste, suivant l'invention, on préférera les sels ferreux, les sels ferriques en milieu alcalin ayant tendance à former de l'hydroxyde ferrique qui catalyse la décomposition du ferrate, et est difficile à éliminer.The iron salt used can be a ferrous salt or a ferric salt. In the synthesis of ferrate in an aqueous medium, ferrous salts are avoided, which are more reducing than ferric salts; by contrast, according to the invention, ferrous salts are preferred, ferric salts in an alkaline medium tending to form ferric hydroxide which catalyzes the decomposition of ferrate, and is difficult to remove.
Par ailleurs l'anion est important. Des anions oxydants, comme du nitrate ferrique, conduisent à des réactions difficilement contrôlables. Des anions réducteurs, susceptibles de venir en compétition avec le fer dans la réaction avec l'hypochlorite, sont bien entendu à éviter. Enfin le sel de fer doit présenter une solubilité dans les bases non négligeable.Besides, the anion is important. Oxidizing anions, such as ferric nitrate, lead to reactions that are difficult to control. Reducing anions, likely to compete with iron in the reaction with hypochlorite, are of course to be avoided. Finally the iron salt must have a significant solubility in bases.
Claims (10)
- A process for the preparation of ferrates of alkali or alkaline-earth metals by the reaction of a hypochlorite on an iron compound which is at most trivalent in the presence of alkaline or alkaline-earth hydroxides, characterised by producing a mixture of an iron (II) or (III) salt and a hypochlorite of alkali or alkaline-earth metal, in the form of powder which passes a first mesh size, forming a first layer of said mixture in powder form in a flat receptacle coupled to a mechanical vibration generator, depositing on said first layer a second layer formed by granules of alkali or alkaline-earth metal hydroxide containing between 10 and 30% by weight of water, the granules being refused at a second mesh size which is markedly larger than the first mesh size, subjecting the receptacle to a vibration effect for a period of from 10 to 60 minutes at less than 40°C so that ferrate is formed in contact with the granules, eliminating the residues in powder form by sieving at a mesh size which is intermediate between the first and second mesh sizes, and eliminating the excess of hydroxide by washing with a substantially anhydrous organic solvent.
- A process according to claim 1 characterised in that, between elimination of the residues in powder form and the washing operation using an organic solvent, the granules are dehydrated by drying in an oven at a temperature of between 105° and 140°C for a period of from 8 to 18 hours.
- A process according to claim 2 characterised by dehydrating the granules at about 120°C for a period of about 12 hours.
- A process according to claim 1 characterised in that the iron salt is a heptahydrated ferrous sulphate.
- A process according to claim 1 characterised in that the alkali or alkaline-earth metal hypochlorite is a calcium hypochlorite.
- A process according to claim 1 characterised in that the alkali or alkaline-earth metal hydroxide is potassium hydroxide in pellet form with 15% by weight of water.
- A process according to claim 1 characterised in that the first mesh size is about 500 micrometers.
- A process according to claim 7 characterised in that the sieving operation for elimination of the residues in powder form is effected with a mesh size of about 1 mm.
- A process according to claim 1 characterised in that the organic solvent is a lower methyl or ethyl alcohol.
- A process according to claim 1 characterised in that the alkali or alkaline-earth metals are contained in the group comprising sodium and potassium on the one hand and calcium and barium on the other hand.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8810750 | 1988-08-09 | ||
FR8810750A FR2635318B1 (en) | 1988-08-09 | 1988-08-09 | PROCESS FOR THE PREPARATION OF ALKALINE OR ALKALINE EARTH FERRATES BY SOLID WAY |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0354843A1 EP0354843A1 (en) | 1990-02-14 |
EP0354843B1 true EP0354843B1 (en) | 1992-11-04 |
Family
ID=9369240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19890402241 Expired - Lifetime EP0354843B1 (en) | 1988-08-09 | 1989-08-08 | Process for the preparation of alkyl or alkaline earth ferrates by the solid phase |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0354843B1 (en) |
DE (1) | DE68903367T2 (en) |
ES (1) | ES2035608T3 (en) |
FR (1) | FR2635318B1 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2654092B1 (en) * | 1989-11-08 | 1992-03-13 | Nancy Ctre Internal Eau | ALKALINE OR ALKALINE-EARTH METAL FERRATES, THEIR PREPARATION AND THEIR INDUSTRIAL APPLICATIONS. |
FR2800056B1 (en) * | 1999-10-22 | 2001-11-23 | Ct Internat De L Eau De Nancy | PROCESS FOR THE SOLID SYNTHESIS OF ALKALINE OR ALKALINE EARTH METAL FERRATES AND FERRATES THUS OBTAINED |
FR2800057B1 (en) * | 1999-10-22 | 2002-10-25 | Ct Internat De L Eau De Nancy | STABILIZED MIXED FERRATES AND METHOD FOR THEIR SYNTHESIS |
FR2832399B1 (en) * | 2001-11-16 | 2004-02-06 | Covalsud Sarl | PROCESS FOR THE PREPARATION OF ALKALINE METAL FERRATES AND NOVEL ALKALI METAL FERRATES GRANULES |
FR2908128B1 (en) * | 2006-11-08 | 2009-01-30 | Stradia Sa | PROCESS FOR THE PREPARATION OF ALKALI METAL FERRATES |
CN108267557A (en) | 2013-10-23 | 2018-07-10 | 哈希公司 | It is analyzed using the COD/TOC of ferrate oxidation method |
CN105917224B (en) | 2013-10-23 | 2018-04-24 | 哈希公司 | For determining the complexes, composition and method of COD |
BR112021026915A2 (en) * | 2019-07-03 | 2022-02-22 | Kemin Ind Inc | Compositions for oxidizing garments and related methods |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2758090A (en) * | 1953-06-05 | 1956-08-07 | Du Pont | Stabilization of ferrates |
JPS5575925A (en) * | 1978-12-04 | 1980-06-07 | Nippon Chem Ind Co Ltd:The | Production of potassium ferrate |
JPS5575926A (en) * | 1978-12-06 | 1980-06-07 | Nippon Chem Ind Co Ltd:The | Production of alkali ferrate |
US4545974A (en) * | 1984-03-16 | 1985-10-08 | Thompson John A | Process for producing alkali metal ferrates utilizing hematite and magnetite |
-
1988
- 1988-08-09 FR FR8810750A patent/FR2635318B1/en not_active Expired - Fee Related
-
1989
- 1989-08-08 DE DE1989603367 patent/DE68903367T2/en not_active Expired - Fee Related
- 1989-08-08 EP EP19890402241 patent/EP0354843B1/en not_active Expired - Lifetime
- 1989-08-08 ES ES89402241T patent/ES2035608T3/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
FR2635318A1 (en) | 1990-02-16 |
EP0354843A1 (en) | 1990-02-14 |
ES2035608T3 (en) | 1993-04-16 |
FR2635318B1 (en) | 1991-07-12 |
DE68903367T2 (en) | 1993-05-19 |
DE68903367D1 (en) | 1992-12-10 |
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